DE3310207A1 - WATER-SOLUBLE OR WATER-DISPERSIBLE RESINY SALTS, THEIR PRODUCTION AND THEIR USE IN COATINGS - Google Patents

Description

... Dr. F. Zumstein Sr. - Dr. E. Ässniann - Dr. R.4Cpen: gsberger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. Klingseisen - Dr. F. Zümstein jun.

Case 3-13858 / ARL 323 / +

Water-soluble or water-dispersible resinous salts, their production and their use in coating compositions

The present invention relates to new water-soluble or water-dispersible resinous salts, a process for their " Manufacture, compositions of matter containing such salts and the Use of such compositions for coating surfaces.

For achieving corrosion-resistant coatings on metal containers the metal surface is usually combined with one in one organic Solvent-dissolved crosslinkable resin formulation coated, after which the coating is heated. The solvent is evaporated in the process and the resin cross-linked. The crosslinking transforms the coating into a tough, flexible and adhesive that adheres to the substrate protective film. During the heating, the solvent is usually evaporated into the atmosphere. Since organic solvents are relative expensive, flammable, and generally environmentally undesirable, there is a need for coatings that are below Use of the lowest possible proportions of such solvents can be applied. Coating compounds with are particularly desirable a high water content.

It has now been found that stable aqueous mixtures, which when Crosslinking coatings with excellent mechanical properties and excellent chemical resistance result from produce new resinous salts containing sulfur or phosphorus. These salts are made from resins by the Mannich reaction with phenolic end groups with an aldehyde and an aminosulfonic acid or an aminophosphonic acid and then partially

or complete neutralization of those introduced by this implementation acidic group (s) produced. The salts can be used together with an aminoplast, a phenol-formaldehyde resin or a blocked polyisocyanate can be used as aqueous coating compositions. May be however, the addition of such co-reactants is not necessary.

The application of Mannich reactions for the production of water-soluble Coating compositions made from epoxides or phenols are known. For example, in the LS patent specification 4,188,312 coating masses that Reaction product of an epoxy resin (i.e. a compound that contains on average more than one 1,2-epoxy group per molecule) with a Mannich base and an alkenylphenol, described. The Mannich base, for its part, is a reaction product of a polyvalent one polynuclear phenol, a secondary amine containing at least one hydroxyalkyl group and formaldehyde. The US patent 4.189.450 describes coating compositions made of an epoxy resin and a Mannich base, produced from a condensed phenol, a at least one secondary amine containing hydroxyalkyl group, formaldehyde and one butadiene or phenolic group containing Isoprene homo- or copolymers. These products do not contain any epoxy groups and are water-soluble in their protonated form.

According to British patent 1,428,835, cationic Polymers by aminomethylation of a p-hydroxystyrene polymer under Use of formaldehyde and a secondary amine that contains alkyl, alkenyl or aromatic groups attached to the N atom or represents a heterocycle with 4 to 6 atoms in the ring. The product can be quaternized, or it can be made from it an acid addition salt can be formed.

In the US Patents 4,000,116 and 4,014,955 crosslinked macromolecular polyethers are described, which by reacting a Mannich base with a polyepoxide and subsequent polyquaterization or by reaction with a compound that has a Hydrocarbon radical bonded chlorine, bromine or iodine atom and

contains at least one epoxy group. The Mannich bases are made from a monomeric bisphenol; dialkylamines and morpholine are used as amines.

According to British patent 1,457,932, epoxide groups are free Polymers produced by reacting a Mannich base with an epoxy resin and then forming a salt. The one on every aromatic ring Mannich base containing one or more cationic hydroxyalkylaminomethyl groups is obtained by reacting a bisphenol, a hydroxyl group-containing one secondary amine or a mixture of such an amine with a further primary or secondary amine and formaldehyde obtain. The resin thus contains these cationic groups on each ring in the residues in the chain which are derived from the Mannich base.

According to similar previously known processes, polymeric bisphenols (reaction products of monomeric bisphenols and epoxy resins) with Formaldehyde and a secondary amine containing hydroxyalkyl groups to form Mannich base bisphenol polymers. According to the US patent 3,994,989, for example, is such a polymeric bisphenol together with a monomeric bisphenol implemented. According to the method according to British patent 1,563,917, the polymeric bisphenol is alone or reacted in a mixture with a monomeric bisphenol. The Mannich Base Bisphenol Polymers only have a cationic hydroxyalkylaminomethyl group on one aromatic ring at the two chain ends on. However, these Mannich base bisphenol polymers are not used directly in coating compositions, but rather through reaction with Epoxy resins further advanced, with bisphenols with an even higher molecular weight.

These pre-extended products have the cationic ones Groups on all aromatic rings that differ from the Mannich base bisphenol polymer derive, i.e. both on the terminal aromatic groups and on such aromatic groups along the Chain.

40

- K-

US Pat. No. 3,936,399 describes phenolic chelating resins which, by means of the Mannich reaction, are obtained from a phenol, iminodiacetic acid and an aldehyde and polycondensation of the product obtained with an aldehyde. The polycondensation product has a pronounced ability to adsorb heavy metals on. No other use is indicated for the intermediate obtained by the Mannich reaction.

The German Offenlegungsschrift 1.445.535 describes the production of alkali-soluble condensation products, which by reaction (a) a phenol or naphthol, (b) formaldehyde or a formaldehyde-releasing substance, (c) a 5- or 6-membered heterocyclic Compound and (d) a mononuclear aromatic carboxylic acid or sulfonic acid, optionally containing hydroxyl or amino groups, an aryloxy fatty acid or an aliphatic polycarboxylic acid in an alkaline, acidic or neutral aqueous medium. Components (a) and (b) are first reacted with one another, and the product obtained is in any order with the components (c) and (d) and optionally additional formaldehyde implemented. Bisphenols, such as bisphenol A, can be used as phenol (a) will. Suitable heterocyclic compounds (c) are. e.g. carbazole, Quinoline and pyrrolidone. Suitable aminosulfonic acids as component (d) are, for example, sulfanilic acid and metanilic acid. The mentioned Condensation products can be found in carbon paper waxes or lithographic compounds or as laking components for basic dyes in flexographic inks.

The German Offenlegungsschrift 2,353,642 describes binders for heat-curing molding compounds that

a) one modified by an aminocarboxylic acid or an aminosulfonic acid Phenol-formaldehyde condensation product and (b) contain a hardener. The condensation product (a) can by Heating 2-6 moles of phenol, 1 mole of amino acid and 0.5-1 mole of formaldehyde, per mole of phenol + amino acid, can be produced. The condensate

tion can be carried out without the addition of a catalyst or in the presence of a base are made, resulting in products similar to novolack. as suitable aminosulfonic acids are called taurine, methyltaurine, sulfanilic acid and aminopropylsulfonic acid. The products are in aqueous Alkali-soluble and are particularly suitable for use in casting compounds. Hexamethylenetetramine is the preferred hardener.

US Pat. No. 4,317,757 describes hot-curable binders for coatings which can be diluted with water. They can be prepared by reacting a polyglycidyl ether of a polyhydric phenol with neutralized sulfanilic acid in a ratio of 0.9 to 1.1 NH equivalents per epoxide equivalent. Together with aminoplasts or phenoplasts, these binders are particularly suitable as crosslinking agents for use in aqueous paints for coating tin cans. The sulfanilic acid is preferably neutralized with an alkali metal hydroxide or a tertiary amine. The reaction between the epoxy resin and the neutralized sulfanilic acid is preferably carried out between 100 and 130 ^° C. for 2 to 7 hours. According to the examples, epoxy resins with a molecular weight of 950 and 370 are used, and the reaction takes place at 124 ° C. for 5 hours.

US Pat. No. 4,332,709 describes binders that can be diluted with water for use in aqueous paints for coating tin cans. They are prepared by reacting a polyglycidyl ether of a polyhydric phenol with an aliphatic amino acid in which at least 50% of the acidic groups have been neutralized with a base, in a ratio of 0.7 to 1.2 NH equivalents per epoxide equivalent. Suitable amino acids are, for example, carboxylic acids and sulfonic acids; however, no specific aminosulfonic acids are mentioned. Suitable bases for neutralization are, for example, alkali metal hydroxides, tertiary amines and quaternary ammonium hydroxides. The epoxy resin is preferably heated for about 15 minutes at 90-100 ⁰ C with the neutralized amino acid. The binders can be used together with aminoplasts or phenolic resins as cross-linking

medium can be used in aqueous coating compositions.

British patent 2,083,044 describes water dispersible modified epoxy resins with terminal amphoteric aminosulfonate groups of the formula -CH -C (R) OH-CHR -NH (R) -R * -SO ~ where R and R "represents a hydrogen atom or a methyl group, R represents a Is hydrogen atom or an alkyl group represented by higher-alkylsulfinyl or higher alkanoyloxy can be substituted, and R, unsubstituted or is alkylene substituted by 2-hydroxyethyl. The modified Resins are made by reacting glycidyl-terminated epoxy resins with an aminosulfonate R NHR SO M, where M represents a cation. As aminosulfonates, the taurine sodium and potassium salts, N- (alkyl) -taurines and 6-aminohexane-1-sulfonic acid preferred. Preferably at least 20% of the glycidyl groups are converted into aminosulfonate groups. The modified resins can optionally used together with an aminoplast, inter alia, in aqueous coating compounds.

The invention relates to new, water-soluble or water-dispersible, sulfur or phosphorus-containing salts of the general Formula I.

R -CH-CH OH

-1

r: h-cho - (- ·.

(κ ⁴ )

4 _

J 4 ^X CH-NR -

η 'ο' R R

»S ^ st

wherein

R is a hydrogen atom or C, -alkyl,

1 ^λ

R is an aliphatic, aromatic or araliphatic two- or trivalent hydrocarbon radical with up to 10 carbon atoms, the one

t- +
may contain further group -Y (M), but preferably none

Has group,

A3

Ι 3 3

R is a hydrogen atom or C, -alkyl, one of R and R is Hydroxyl group and the other a hydrogen or halogen atom,

4th
C1-4 alkyl or C1-4 alkenyl and R, independently of one another, denote a hydrogen or halogen atom, C1-4 alkyl or C1-4 alkenyl, R to a ring carbon atom in the ortho or para position to the hydroxyl

3 3
Representing group R or R. is bonded and a hydrogen or

2 2 8 halogen atom, C 1, -alkyl, C, -alkenyl, -CH (R) 0H, -CH (R) 0R or a Group of formula II

Represents -CH - N - R ¹ - (Υ ^ϋ ~) (M ⁺ ) (II),

i ₂ 1 ^{s st}

R R

R is the remainder of a polyepoxide after removal of (m + p) 1,2-epoxide groups means,

each R is independently a hydrogen atom or a covalent one Represent a bond to the group R, wherein a cycloaliphatic ring is formed by one or more aliphatic, cycloaliphatic and / or heterocyclic groups can be substituted, but is preferably unsubstituted,

R C -alkyl or alkoxyalkyl with 1-6 carbon atoms each in the alkoxy and alkyl,

9 ^1-6
R is the residue of a monohydric phenol, a secondary monoamine or a monocarboxylic acid after removing the hydrogen atom of the phenolic hydroxyl group, the secondary amino group or the carboxylic acid group,

m 1, 2, 3 or 4,

η zero or 1 and

ρ means zero or 1, so that (m + p) at least 2 and at most 4

t is 1 or 2,

X C "-alkylene, C -alkylidene, a carbonyl or sulfonyl group, means an oxygen or sulfur atom or the direct bond,

M is a hydrogen ion, one of an alkali metal, ammonia, or one Amine-derived cation, including quaternary ammonium cations, or a valence of a polyvalent cation with which Provided that at least 25% of the M ions are cations of the type mentioned

/ 14

- ST-

s is 1 or 2 and

Y a Λιιίοη dor formulas I.ΓΤ, TV odor V

»Β Il JO Il O

-s '(III), -p' (IV) or -P (V)

N) Oil O

represents.

The R represent preferably em hydrogen or llalogen.-itoin, C, -alkyl or C ₀ , -alkenyl. The R each preferably denote a hydrogen atom or a covalent bond to the group R, an unsubstituted cycloaliphatic ring being formed.

6 Preference is given to salts of the formula I, where R is a radical with a represents average molecular weight from 1,000 to 5,000, and those in which (m + p) is 2. Particularly preferred are those salts in which R is a hydrogen atom and R is C 1, -alkylene, C ^ -alkylidene, arylene, Aralkylidene or aralkylene with up to 10 carbon atoms mean. Digits R,

3 4 5
If R, R or R are halogen atoms, they are preferably chlorine or bromine atoms.

Salts of the formula I are also those of the formulas VI or VII

St -

J- / \ / ~ \ -OCU SJcH -R ¹⁰ -CH £ Ici

^R (

4 Ta 53 \ _(yi)

/ ^T 4 ^T 4

-N-CH R (R)

II ₂
RR

ι A

E ³ -.

st

-Ck R ⁴ Y ₂

* · · ' V-OCH ₀ CHCH ₀ -R ° -CH ₀ CHCH ₀ R ⁹ "c / 2 2 Z 2 (R ⁴ ),

(VII)

1233459 + preferred, wherein R, R, R, R, R, R, R, R, X, Y, M, s and t die have the meaning given above and

R is the remainder of an aliphatic, cycloaliphatic or aromatic Diglycidyl ethers or diglycidyl esters after removing both glycidyl groups represents.

R in the compounds of the formulas VI and VII preferably represents a Group of formula VIII

. (AS.

'ΐ:

(R ⁴ )

'τ:

0-

(VIII)

daring

4th
R and X have the meaning given above and q is zero or an integer from 1-20, in particular 2-10.

Salts of the formulas I, VI and VII in which R is a hydroxyl group are very particularly preferred
each represent a hydrogen atom.

3 2 4

in which R is a hydroxyl group, as well as those in which R and R

The invention also relates to a process for the production of water-soluble or water-dispersible resinous salts by adding a phenolic-terminated resin of the formula IX

I ¹ MI-UI
H

- K -

JP

CII-CM OH

(R ^A ).

(IX),

4 6 7 9
where R, R, R, R, X, m, η and ρ have the meaning given above, with the proviso that at least one of the two carbon atoms is in the ortho position or the carbon atom in the para position to the one bearing the specified phenolic hydroxyl group Carbon atom is unsub.4l-i.tuated,

■ f.
in the presence of an M ion-releasing agent with an aldehyde of the formula X

R ² CHO (X)

and an aminosulfonic acid or an aminophosphonic acid of the formula XI

HN-R -YH I R

(XI)

2 +
converts, where R, R and M have the meanings given above, R _{1 is} an aliphatic, aromatic or araliphatic di- or droiwcirLigüu hydrocarbon residue with up to 10 carbon atoms thirst Lit, which has a free phosphonic or sulfonic silur group of the formula -> S (: 0) y3H or -P (: O) (OH) _, and Y don Reist ο Liier represents sulfonic or phosphoric acid after HntCern of a hydrogen atom, ie -SO - or -PO ₂ H-.

The reaction is preferably carried out by heating the reactants in the presence of a sufficient amount of base for at least partial neutralization, any free acid present and possibly in the presence of a surface-active agent as phase transfer

-W-

Catalyst made. An inert solvent is also generally used. The reaction temperature is preferably between 60 and 180 ^° C., in particular 75 and 140 ^° C. In general, the reaction is complete after 15 minutes to 8 hours. Suitable inert solvents are, for example, hydrocarbons, ethers, alcohols and esters, such as toluene, xylene, tetrahydrofuran, butanols, ethyl acetate and, above all, 2-butoxyethanol and 2-ethoxyethanol. Suitable bases for the at least partial neutralization are, for example, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonia, triethylamine and triethanolamine. Preferred bases are 2- (dimethylamino) -2-methyl-propan-1-ol and 2- (dimethylamino) ethanol.

Is the implementation of the resins of the formula IX with phenolic end groups with the aldehydes of the formula X and the aminosulfonic or aminophosphonic acids of the formula XI in the presence of a suitable one Alcohol, e.g. those of the type mentioned above, carried out so

5 2 2 8

groups R = -CH (R) 0H can be etherified to groups -CH (R) 0R.

In general, 0.3 to 2.0 moles of the amino acid of the formula XI used per mole of phenolic hydroxyl groups in the resin of formula IX. The aldehyde of the formula X is expediently used in excess used, especially 1.1 to 4.0 moles of aldehyde per mole of acid of the formula XI. The products obtained in this way are at room temperature improved storage stability. The aldehyde of the formula X is preferably formaldehyde, which is expediently extracted in situ Paraformaldehyde is formed.

Suitable amino acids of the formula XI are e.g. sulfanilic acid, taurine, Orthanilic acid, 2-aminobenzene-l, 4-disulfonic acid and phosphorus acids of the formula XII

\ -R ^U

OH

-NH (XII),

OH ²

worj.li

R cine lcovalue bond or C, -alkylene,

12th
R C., -alkyl, C _f -aryl or a group of the formula XIlL

I.
0 = 1 '(OH) «(XIII) and

13th
R is a hydrogen atom, C, -alkyl or C -aryl, or in which R and R together with the carbon atom to which

13 they are bound to form an aromatic ring and R does not exist.

The Har / .e used ala Auagang.ssprodukte with terminal phono groups of the formula IX can be obtained by methods known per se by reacting a polyepoxide, preferably a diepoxide, with a dihydric phenol. The polyepoxide is extended by reacting it with the two hydroxyl groups of the dihydric phenol. To produce products with at least one terminal phenolic group, the dihydric phenol and the polyepoxide must be present in molar amounts. The molar ratio of polyopoxide to dihydric phenol is generally between 1: 1.02 to 1: 1.6 and particularly between 1: 1.1 to 1: 1.5. The advancement by heating the reactants at 100-200 ⁰ C in the presence of a base, for example a tertiary amine is preferred and particularly an alkali metal made. An inert solvent can also be used.

The dihydric phenol used for the advancement can be mononuclear, e.g., a hydroquinone, but is preferably a Bisphenol, especially one of the formula XIV

^H0 "* x) ·" ^χ ~ · χ) · " ^0Η · = ·

4th
worm X and R have the meaning given above, such as bis (4-hydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl) propane.

Preferred polyepoxides for the production advancement reaction of the starting products of the formula IX are those which have two terminal groups of the formula XV

(XV)

which are bonded directly to an 0, N or S atom.

Examples of such resins are polyglydicyl esters which, by reacting one containing two carboxylic acid groups per molecule, may be mentioned Compound with epichlorohydrin or glycerol dichlorohydrin can be obtained in the presence of a base. Such polyglycidyl esters can derived from aliphatic polycarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid and dimerized linoleic acid; of cycloaliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid, as well as aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.

Further examples are polyglycidyl ethers, which by reaction of a per molecule containing at least two free alcoholic or phenolic hydroxyl groups with epichlorohydrin or Glycerol dichlorohydrin obtained in a basic medium or in the presence of an acidic catalyst and subsequent treatment with base

will. These ethers can be prepared from: acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol and poly (oxypropylene) glycols, propane-1,3-diol, butane-1,4- dio1, poly (oxytetramethylene) glycols, pentane-1,5-diol and polyepichlorohydrins; cycloaliphatic alcohols such as resorcitol, quinitol, bis- (4-hydroxycyclohexyl) methane, 2,2-bis- (4-hydroxycyclohexyl) propane and 1,1-bis (hydroxymethyl) -cyclohex-3-ene; of alcohols with aromatic nuclei, such as N, N-bis (2-hydroxyethyl) aniline and p, p ^l -bis (2-hydroxyäthylamino) diphenylmethane. Such ethers can also be obtained from mononuclear phenols such as resorcinol and hydroquinone, or from polynuclear phenols such as bis (4-hydroxyphenyl) methane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis - (4-hydroxyphenyl) propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane and 2,2-bis- (2-allyl-4-hydroxyphenyl) propane.

Examples of poly (N-glycidyl) compounds are those made by Dehydrochlorination of the reaction products from epichlorohydrin with amines with two amine hydrogen atoms, such as aniline, n-butylamine and bis- (4-methylaminophenyl) methane, obtained; also N, N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethylene urea and 1,3-propylene urea, or hydantoins such as 5,5-dimethylhydantoin.

Examples of poly (S-glycidyl) compounds are di-S-glycidyl derivatives of dithiols, such as ethane-1,2-dithiol and bis (4-mercaptomethylphenyl) ether. It is also possible to use polyepoxides in which the 1,2-epoxy groups are bonded to different heteroatoms are, for example, the glycidyl ether glycidyl ester of salicylic acid, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin and 2-glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoin-3-yl) propane.

It is also possible to use polyepoxides with non-terminal epoxy groups such as vinylcyclohexene dioxide, limonene dioxide, dicyclopenta-

-IS--

2 7 3 5
diene oxide, 4-oxatetracyclo [6.2.1.0, 0] -undec-9-yl-glycidyl ether,

2 7 3 5
the bis (4-oxatetracyclo- [6.2.1.0 *, 0 '] undec-9-yl ether of ethylene glycol, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate and its 6,6'-dimethyl derivative, the Bis (3,4-epoxycyclohexanecarboxylate) of ethylene glycol and 3- (3,4-epoxycyclohexyl) -8,9-epoxy-2,4-dioxaspiro [5,5] undecane.

If desired, mixtures of different diepoxides can also be used will. Polyepoxides with more than two epoxy groups can be extended if desired. However, it is to the epoxy skilled in the art known that such pre-extensions are rather difficult because of the risk of gelation.

Preferred diepoxides are diglycidyl ethers and esters. Particularly preferred diepoxides are the diglycidyl ethers of 2,2-bis (4-hydroxyphenyl) propane and bis (4-hydroxyphenyl) methane with a 1,2-epoxide content of more than 1.0 equivalent per kilogram.

The dihydric phenol can be used alone or, if desired, in the presence a compound which does not react further with one of the terminal epoxide groups of the polyepoxide and thus an additional one Chain extension prevented from being used. Suitable chain terminators include secondary monoamines, monocarboxylic acids and especially monohydric phenols; p-tert-butylphenol is particularly preferred. The chain terminator must be used in such an amount that at least one of the epoxy groups per average molecule of the Polyepoxide remains free for reaction with the dihydric phenol.

As already mentioned, the salts according to the invention can be in the form of heat-curable ones Compositions of substances used for surface coatings will.

The invention thus further relates to hot-curable compositions of matter, containing 100 parts by weight of a salt of the formula I, based on the solids content (as defined below) and 2 to 200 parts by weight, preferably 25-150 parts by weight, based on the solids content, of an aminoplast, a phenol-formaldehyde resin or a blocked polyisocyanate, the aminoplast or the phenol-formaldehyde resin having at least two groups of the formula XVI

14th
-CH ₂ OR (XVI)

have which are attached directly to amide nitrogen atoms or to carbon atoms

14th of a phenolic ring, where R em hydrogen toff atom or is C1-alkyl.

Contain such compositions of matter in suitable application forms generally also water and a smaller proportion, compared to the proportion of water, of an organic solvent such as ether, Alcohols, ketones or esters, especially 2-butoxyethanol or 2-ethoxyethanol.

Suitable methylolated compounds for such compositions of matter are e.g. urea-formaldehyde condensates, aminotriazine-formaldehyde condensates, especially melamine-formaldehyde and benzoguanamine-formaldehyde condensates, and phenol-formaldehyde condensates. If desired, these can be etherified; for example, the corresponding n-Butyl ether can be used. In some cases they are methylolated compounds and their ethers are not water-soluble per se or dispersible in water. The addition of a compound of the formula I favors the dispersion or solution of such materials in water, stable solutions or dispersions of the mixtures being obtained.

As examples of suitable blocked polyisocyanates (i.e. of polyisocyanates which are dispersed in water at room temperature are stable, but react with the compound of formula I when heated) the following may be mentioned: di- and poly-isocyanates, capped with Caprolactam, an oxime (e.g. cyclohexanone oxime), a monohydric phenol (e.g. phenol, p-cresol and p-tert-butylphenol) or a Monohydric aliphatic, cycloaliphatic or araliphatic alcohol (e.g. methanol, n-butanol, decanol, 1-phenylethanol, 2-ethoxyethanol and 2-n-butoxyethanol). Examples of suitable aromatic diisocyanates are m-phenylene; 1,4-naphthylene, 2,4- and 2,6-tolylene and 4,4'-methylene-bis (phenylene) -di-isocyanates and their prepolymers with glycols (e.g. ethylene glycol and propylene glycol), glycerine, Trimethylolpropane, pentaerythritol, diethylene glycol, and adducts of alkylene oxides with the aliphatic di- and polyvalent ones mentioned Alcohols.

The substance mixtures can by heating to 100 to 275 ° C, especially 150 to 225 ° C, for 30 seconds to 1 hour, especially 2 to minutes, are cured.

The mixtures of substances can also be other water-soluble or in water contain dispersible film-forming substances, such as alkyd resins and acrylic resins. The proportion of such materials can continue within Limits vary, but should not be so great that the advantageous properties of the compositions of matter according to the invention are affected covered. In general, additives of up to 50% by weight, and preferably not more than 30% by weight, are used, with these percentages relate to the solids content of the materials.

The term "solids content" is used in the description and the claims understood the residual percentage obtained after adding 1 g of substance in an open dish 5 cm in diameter

- ier-

Atmospheric pressure. heated in an oven at 120 ° C. for 3 hours became.

5 2

It has been found that when R in formula I denotes a group -CH (R) 0H, the salts without the addition of an aminoplast, a phenol-formaldehyde resin or a blocked polyisocyanate can be cured.

The present invention also includes a method for surface coating, by putting a composition of matter on the surface of the type described above or in the absence of an aminoplast of a phenol-formaldehyde resin or a blocked polyisocyanate

5 2

a salt of the formula I applied, in which R is a group -CH (R) 0H,

and the coated surface to a temperature between 100 and 275 ° C, especially 150 and 225 ° C, heated and with it the composition or the salt hardens. The heating is preferably carried out for 30 seconds to 1 hour, in particular 2 to 30 minutes.

Finally, the invention relates to the one according to the invention Material composition coated surfaces, both in the hardened as well as in the non-hardened state. Such surfaces are preferably made of primed or unprimed metal, especially Ferrous metals. However, they can also be made of wood or heat-resistant synthetic materials.

The compositions of matter can be dipped, brushed, rolled, Spraying (including electrostatic spraying processes) Electrocoating or other conventional methods can be applied. If desired, they can also contain other additives, such as Pigments or dyes, fillers such as calcium carbonate, calcium sulfate, barium sulfate and magnesium silicate; surfactants, Superplasticizers and plasticizers. You can also use strong acids such as aromatic sulfonic acids or salts thereof as catalysts with amines or ammonia.

The invention is illustrated in more detail by the following examples. In this, percentages are always total percentages.

The starting materials used in the examples can be used as follows getting produced:

Phenol I.

760 g of epoxy resin I, ie a liquid diglycidyl polyether of 2,2-bis- (4-hydroxyphenyl) propane (epoxy group content 5.25 equiv./kg), 684 g of 2,2-bis- (4-hydroxyphenyl) propane and 1, 6 of a 10% strength aqueous sodium hydroxide solution are stirred and heated ^{to 160 ° C. under nitrogen.} The molar ratio of epoxy resin to bisphenol is 1: 1.5. An exothermic reaction sets in and the temperature of the mixture rises spontaneously to 197 ° C. The mixture is ^{cooled to 180 °} C. and stirred at this temperature for a further 3 hours. Phenol I, a resin with terminal phenolic hydroxyl groups, a negligible epoxide group content (not more than 0.02 equiv./kg) and an average molecular weight of 1370 is obtained.

Phenol II

359 g of epoxy resin I, 246 g of 2,2-bis (4-hydroxyphenyl) propane, 20 g of p-tert-butylphenol and 0.39 g of a 10% strength aqueous sodium hydroxide solution are stirred and heated ^{to 180 ° C. under nitrogen.} The molar ratio of epoxy resin to bisphenol to monohydric phenol is 1: 1.14: 0.14. An exothermic reaction sets in, and the temperature of the mixture rises spontaneously to 2O7 ° C.The mixture is cooled to 180 ⁰ C and stirred for 3.5 hours at this temperature. Phenol II, a resin with terminal phenolic hydroxyl groups, a negligible epoxy group content and an average molecular weight of 1,880 is obtained.

Phenol III;

200 g of S ^ -epoxycyclohexylmethyl-S '^' - epoxycyclohexanecarboxylate (epoxy group content 7.00 equiv./kg), 199.5 g of 2,2-bis (4-hydroxyphenyDpropane and 2.4 g of a 50% aqueous tetramethylammonium chloride solution) . stirred and heated to 120 ⁰ C. the molar ratio of epoxy resin to bisphenol is 1: 1.25 an exothermic reaction sets in, and the temperature of the mixture rises spontaneously to 132 ° C. the mixture is cooled to 120 ⁰ C and.. Stirred for 2 hours at this temperature and then for 3 hours at 160 ^° C. This gives phenol III, a resin with terminal phenolic hydroxyl groups, a negligible epoxy group content (0.08 equiv./kg) and an average molecular weight of 1220. Phenol IV:

114.3 g of epoxy resin I, 44 g of hydroquinone and 1 g of a 50% aqueous tetramethylammonium chloride solution are stirred and heated to 130 ⁰ C. The molar ratio of epoxy resin I to hydroquinone is 1: 1.33. An exothermic reaction begins and the temperature of the mixture rises spontaneously to 190 ^° C. The mixture is ^{cooled to 160 °} C. and stirred at this temperature for 3.5 hours. Phenol IV, a resin with terminal phenolic hydroxyl groups, a negligible epoxide group content (not more than 0.02 equiv./kg) and an average molecular weight of 1520 is obtained.

Phenol V:

100 g of epoxy resin II, ie a solid diglycidyl polyether of 2,2-bis- (4-hydroxyphenyl) propane (epoxy group content 1.40 equiv./kg), 70 g of 2-butoxyethanol and 2.1 g (0.035 mol) of acetic acid are stirred , heated to 120 ⁰ C and held at 120 ⁰ C for 4 hours. After this time the epoxy group content has dropped to 0.58 equiv./kg. 24 g of 2,2-bis- (4-hydroxyphenyl) propane and 0.2 g of a 10% strength aqueous sodium hydroxide solution are then added. The mixture is ^{heated to 170 °} C. under nitrogen and kept at 170 ^° C. for 6 hours. A solution of phenol V in 2-butoxyethanol is obtained, ie a resin with terminal phenolic hydroxyl groups and one negligible

Epoxy group content.

Aminoplast I: This is a water-soluble, methylated hexamethylolmelamine resin with 100% solids content, which contains on average 4.0 methoxymethyl radicals per aminotriazine core and has a viscosity of 10 Pa s at 25 ° C.

Phenoplast I: This is a commercially available butylated phenol-formaldehyde resin in the form of a solution in n-butanol (56% solids content) which contains a small amount of toluene. This resin is neither soluble nor dispersible in water.

Blocked isocyanate I: 43.9 g (0.025 mol) of a mixture of 2,4- and 2,6-diisocyanatotoluene (ratio 4: 1) is stirred in a reactor and slowly added with 71.5 g (0.55 mol contains) of 2-ethylhexanol, of 2 drops of dibutyltin dilaurate (catalyst) was added while the temperature is maintained below 60 ⁰ C.

2-Amino-1-phenylethyl-phosphonic acid: produced from cinnamic acid amide and dialkylphosphite and then treated with sodium hypobromite and hydrolyzed as described in Chemical Abstracts, 73_ »87977c.

I-Aminoäthyliden-bis- (phosphonic acid) and aminophenylmethylene-bis (phosphonic acid): These compounds are produced by the action of phosphorus tr! halide on acetonitrile or benzonitrile and subsequent hydrolysis according to Chemical Abstracts, ^ 53_, 21814e.

Free formaldehyde is determined by the following method: Weigh about 1.5 g of the resin precisely and place it in a conical flask given. Add 30 ml of distilled water and mix the contents thoroughly. Then 3 drops of thymolphthalein indicator are given and the mixture is neutralized with 0.1 N HCl or sodium hydroxide if necessary. The mixture is cooled in ice, and 25 ml (12.5% by weight) of ice-cold sodium sulfite solution are added.

The mixture is then shaken vigorously and washed with 0.1 N HCl until Disappearance of the blue color titrated. Percent free formaldehyde = titer (ml) χ 0.1 N HCl χ 3.001

Weight of the sample (g)

Example 1: A solution of 50.0 g (0.036 mol) of phenol I in 16.7 g of 2-butoxyethanol was mixed with 8.7 g (0.050 mole) of sulfanilic acid and heated to 100 ⁰ C. After 30 minutes at 10O ⁰ C the mixture is cooled to 80 ⁰ C and there are

5.0 g (0.15 mol) of paraformaldehyde (91% active content) and 7.4 g (0.050 mol) of an 80% strength aqueous solution of 2-dimethylamino-2-methylpropan-1-ol were added. This solution is carefully ^{heated to 120 °} C. and kept at this temperature for 3 hours. After this time, the measured proportion of free formaldehyde has dropped to 0.78%. The product has a solids content of 62% and can be completely diluted with water.

2

The product corresponds essentially to the formula I, in which R, R, R, R and R hydrogen, R p-phenylene, R -OH, R hydrogen or -CH.OH in ortho-position to R and R a radical with structural elements of formula XVII

CH " "\ -OCH ₂ r / * 1TT ^ U · - · CH / "1TT Λ ^ f Vc - ^ * OH ι ³ / · " CH ₃ ' CH ₃ - =

(XVII)

mean, where u averages 2.3, m is 2, ρ is 0 and n, s and t are each 1, X isopropylidene para to R, Y

+ represent a group HOCH C (CH) NH (CH).

~ S0 and M 3

Example 2: A solution of 50.0 g (0.027 mol) of phenol II in 39 g of 2-butoxyethanol was mixed with 8.7 g (0.050 mole) of sulfanilic acid and heated to 100 ⁰ C. 3.9 g (0.026 mol) of an 80% strength aqueous solution of 2-dimethylamino-2-methylpropan-1-ol are then added and the mixture is kept at 100 ^° C. for 30 minutes. Subsequently, 3.3 g (0 , 10 mol) of paraformaldehyde (91% active content) are added and the mixture was heated an additional hour at 10O ⁰ C. the temperature is then raised to 120 ⁰ C and heated for an additional 2.5 hours. After this time, the measured free formaldehyde content has dropped to 0.43%. The product has a solids content of 59% and can be completely diluted with water. The product essentially corresponds

2 3 4 7 1

of the formula I, in which R, R, R, R and R are hydrogen, R p-phenylene,

3 5 6

R -OH, R hydrogen or -CH OH ortho to R and R a radical with structural elements of the formula XVII, where u is average

9 borrowed 4.0, (m + p) is 2, n, s and t are each 1, R p-tert-butylphenoxy, X isopropylidene para to R, Y "SO ,, and M Represent HIGH C (CH) NH (CH).

£ - ^ 3 Δ. ^ j Z-

Example 3: A solution of 50 g (0.027 mol) of phenol II in 39 g of 2-butoxyethanol is mixed with 6.3 g (0.050 mol) of taurine and 4.5 g (0.050 mol) of 2- (dimethylamino) ethanol and added 120 ⁰ C heated. After 30 minutes at 120 ⁰ C, the mixture is cooled to 100 ° C, followed by 3.3 g (0.10 mole) of paraformaldehyde (91% active content) are added. The solution is carefully ^{heated to 120 °} C. and kept at this temperature for 3 hours. After this time, the measured free formaldehyde content has dropped to 0.45%. The product has a solids content of 59% and can be completely thinned with water.

2 3 The product essentially corresponds to the formula I, in which R, R, R

4 7 13 5

R and R hydrogen, R -CH CH -, R -OH, R hydrogen or

3 6

-CH OH ortho to R and R is a radical with structural elements of the formula XVII mean, where u averages 4.0, (m + p) is 2,

9
n, s and t are each 1, R p-tert-butylphenoxy, X isopropylidene para

3 t- - + ⁺
to R, Y — SO and M HIGH CH ₂ NH (CH).

Example 4: 50 g (0.041 mol) of phenol III are mixed with 40 g of 2-butoxyethanol and heated to 120 ⁰ C. After the phenol has completely dissolved, the solution is ^{cooled to 100 °} C., and 8.7 g (0.050 mol) of sulfanilic acid, 4.6 g (0.050 mol) of 2- (dimethylamino) ethanol and 5.0 g (0, 15 mol) 91% paraformaldehyde was added. The mixture is carefully ^{heated to 140 °} C. and kept at this temperature for 4 hours. After this time, the measured free formaldehyde content has dropped to 0.26%. The product has a solids content of 58% and can be completely diluted with water. The product

2 3 4 essentially speaks of the formula I, in which R, R, R and R are water

13 5
substance, R p-phenylene, R -OH, R hydrogen or -CH OH ortho

o "7 aa

R, R form a covalent bond with R and R together with the given Hydroxyethylene group is a group essentially of the formula XVIII

CH

• 0- VC-β ' ^x # -0

T -T-CH OCO- * T CH * T -f-CH OCO- * T

h / v "V h / v 'V \ h

(XVIII)

mean in which each terminal bond of the groups -CH "OCO-itself is in the 3- or 4-position to the specified hydroxyl group,

m is 2, ρ is zero and n, s and t are each 1, X isopropylidene para to R,

t- - + +
Y represent -SO ₃ and M represent HOCH ₂ CH ₂ NH (CH ₃ ) ₂ .

Example 5: 22.5 g (0.015 mol) of phenol IV is mixed with 40 g of 2-butoxyethanol and heated to 120 ⁰ C. After the phenol has completely dissolved, the solution is ^{cooled to 100 °} C. and 4.3 g (0.025 mol) of sulfanilic acid and 2.3 g (0.026 mol) of 2- (dimethylamino) ethanol are added. The mixture is ^{kept at 100 °} C. for 1.5 hours and then 2.5 g (0.075 mol) of 91% paraformaldehyde are added. Subsequently, the temperature of the mixture is increased to 140 ⁰ C. This temperature is held for 4 hours. After this time, the measured free formaldehyde content has dropped to 0.30%. The product has a solid

-K-

content of 42.3% and can be completely diluted with water. The product

2 3 4 corresponds essentially to the formula I, in which R, R, R, R and R

1 3 5

Hydrogen, R p-phenylene, R -OH, R hydrogen or -CH OH ortho

for R and R a radical containing 2,2-bis ~ (4-hydroxyphenyl) propane, -CH ₂ CH (OH) CH and p-phenylenedioxy groups, m is 2, ρ and η zero and s and t each 1, Y * ¹ "-SO ~ and M ⁺ HIGH CH ₂ NH (CH ₃ ).

Example 6: A solution of 20 g (0.010 mol) of phenol II in 20 g of 2-butoxyethanol is treated with 1.5 g (0.0075 mol) of 2-amino-1-phenylethylphosphonic acid (ie the compound of the formula XII in which R is methylene ,

12 13

R is phenyl and R is hydrogen), 1.5 g (0.017 mol) of 2- (dimethylamino) ethanol and 0.8 g (0.024 mol) of 91% paraformaldehyde are mixed and heated to 120.degree. After 4 hours at 120 ^° C., the measured content of free formaldehyde has dropped to zero. The product has a solids content of 52% and can be completely diluted with water. The product corresponds essentially to the formula I, wherein

R, R, R ₁ , R and R hydrogen, R 0, H-CHCH- R -OH, R water-1 ₃ gb 6 ζ

substance or -CH OH ortho to R and R are structural elements of the formula XVII having radical mean, wherein u mean 4.0

9, (m + p) is 2, η and s are each 1 and t is 2, R is p-tert-butylphenoxy, X isopropylidene para to R, Y is a group of the formula V and

+ +
M is HOCH ₂ CH NH (CH ₃ ).

Example 7: A solution of 5 g (0.0036 mol) of phenol I in 11.7 g of 2-butoxyethanol is mixed with 0.8 g (0.004 mol) of 2-amino-1-phenylethylphosphonic acid, 0.4 g (0.004 mol) 2- (dimethylamino) ethanol and 0.4 g (0.012 mol) of 91% paraformaldehyde mixed and heated to 120 ⁰ C. After 4 hours at 120 ⁰ C, the content of free formaldehyde has dropped to zero and the product is completely dilutable with water.

2 The product corresponds essentially to the formula I, in which R, R, R, R and R hydrogen, R C, H CHCH -, R -OH, R hydrogen or -CH OH ortho to R and R are a structural element of the formula XVII

denote the remainder, where u is on average 2.3, ρ zero is, m is 2 and n, s and t are each 1, X isopropylidene para to R,

t- j / ° "+ +
YO = P and M represent HOCH CH NH (CH).

OH

Example 8: A solution of 8 g (0.006 mol) of phenol I in 8 g of 2-butoxyethanol is treated with 1.2 g (0.006 mol) of 1-aminoethylidene-bis (phosphonic acid) (ie the compound of the formula XII in which R is a

12 13

covalent bond, R is a group of formula XIII and R is methyl), 2.2 g (0.025 mol) of 2- (Dimethylamine) ethanol and mixed 0.6 (0.018 mol) of 91% paraformaldehyde and heated to 120 ⁰ C. After one hour at 120 ^° C., the measured content of free formaldehyde has dropped to zero and the product can be completely diluted with water. The product essentially corresponds to

2 3 4 7 1 '

Formula I, wherein R, R, R, R and R are hydrogen, R -C (CH) "", R

5 3 6

-OH, R hydrogen or -CH OH ortho to R and R are structural elements of the formula XVII, where u averages 2.3, ρ is zero, m is 2, η is 1, s and t

3 are 2 each, X isopropylidene para to R, Y

¹ Z ⁰ "+ +

O = P and M are HOCH ₉ CH ₉ NH (CH).

Example 9; A solution of 20 g (0.015 mol) of phenol I in 20 g of 2-butoxyethanol is mixed with 4.0 g (0.015 mol) of aminophenylmethylene-bis (phosphonic acid) (ie the compound of the formula XII in which R is

12 13

covalent bond, R is a group of the formula XIII and R is phenyl), 5.4 g (0.060 mol) 2- (dimethylamino) ethanol and 1.5 g (0.045 mol) 91% paraformaldehyde are mixed and heated to 120 ° C. After one hour at 120 ^° C., the measured content of free formaldehyde has dropped to zero and the product can be completely diluted with water. The product corresponds essentially to the formula I, in which R, R, R, R and R are hydrogen, R -C (C, H) -, R -OH,

5 3 6

R is hydrogen or -CH OH ortho to R and R is a radical containing structural elements of the formula XVII, in which u is on average 2.3, ρ is zero and m, s and t are each 2, X isopropylidene

para to R ³ , Y ^ O = K and M ⁺ HIGH CH NH (CH).

Example 10: 50 g of the solution of phenol V are mixed with 6.3 g (0.050 mol) of taurine and 4.2 g (0.047 mol) of 2- (dimethylamino) ethanol and heated to 100 ⁰ C. When 100 ° is reached, 3.3 g (0.1 mol) of 91% paraformaldehyde are added. Then further heated to 140 ⁰ C. The mixture is kept at 140 ° C. for 3 hours. At this time the measured free formaldehyde content has dropped to 0.6%. The product has a solids content of 62.5% and can be completely diluted with water. The product essentially corresponds to

2 3 4 7 1

Formula I, in which R, R, R, R and R are hydrogen, R -CH CH -,

"_ I 3 6

R -OH, R is hydrogen or -CH ₂ OH ortho to R and R is a radical having structural elements of the formula XVII, wherein u

9 averages 3.9, (m + p) is 2, η is 1, R CH COO-,

3 + + ^J

X is isopropylidene para to R and M is HOCH CH NH (CH).

Example 11: A solution of 64.4 g (0.046 mol) of phenol I in 21.5 g of 2-butoxyethanol was mixed with 10.4 g of (Q, 06 mol) of sulfanilic acid and heated to 12O ⁰ C. After 30 minutes at 12O ⁰ C the mixture is cooled to 100 ⁰ C and treated with 6 g (0.18 mol) of 91% paraformaldehyde and 5.3 g (0.06 mol) of 2- (dimethylamino) ethanol. This solution is carefully ^{heated to 140 °} C. and kept at this temperature for 4.5 hours. After this time, the measured free formaldehyde content has dropped to 0.9%. The product has a solids content of 66.5% and can be completely diluted with water.

2 The product essentially corresponds to the formula I, in which R, R, R,

4 7 χ 3 5

R and R hydrogen, R p-phenylene, R -OH, R hydrogen or

-CH ₂ OH para to R and R are a radical having structural elements of the formula XVII, in which u is on average 2.3, m is 2,

η is 1, X is isopropylidene para to R and M is HOCH CH NH (CH).

3H

Examples 12-13; Coating materials are produced by mixing the products according to Example 1 or 3 with Aninoplast I in a ratio of 70:30, based on the solids content. The solutions obtained are diluted with water to a viscosity of 20-30 mPa s and applied to tin-coated steel plates by means of spin coating so that a layer 2 ^ m thick is formed. The plates are then heated to 215 ° C for 3 minutes and tested. The results are given in Table I.

Examples 14-15: By mixing the products according to example 3 or 7 with phenoplast I in a ratio of 70:30, based on the solids content, coating compositions are produced. The solutions obtained are diluted with water to a viscosity of 20-30 mPa s and applied to aluminum or tin-coated steel plates by means of spin coating so that a 2-4 / am thick layer is formed. The plates are then ^{heated to 200 °} C. for 15 minutes and tested. The results are given in Table I.

Table I.

test Examples 13th Al- 14th Al- L5 Zn- 12th plate Zn- plate plate Well plate Well Well
75% Well
70% Well
70% Rub test with MEK ¹
2)
Wedge bending test
unchanged at Well
70% Well Well Well Well Pasteurization
in water 75 ° C /
40 minutes Well - Well Well Well Well 3% acetic acid.
100 ° C / l, 5 hours ^; - - unsuccessful
gend 3% acetic acid
100 ° C / 6h ' -

- 26 - The sign "(-) means that the test was not carried out.

1) Rub test with MEK: The coated surface undergoes 50 double rubs subjected to soaked with methyl ethyl ketone cotton wool. Afterward if the surface is checked for peeling or softening of the coating, "good" means that no change occurs.

2) Wedge bending test: The impact bending of the test specimens is performed using a 10 cm long bending mandrel with an outside diameter of 6 mm determined at one end and a tapering other end. The length of the test piece is then determined in percent which does not peel off the coating.

3) Pasteurization and Cooking Test. The samples are during the specified time heated in water or acetic acid at the specified temperature. The surfaces are then checked for any Impairments examined, "good" means no impairment or damage.

Example 16: 13.8 g of the product according to Example 2, 2.0 g of the blocked isocyanate I, 0.6 g of dibutyltin dilaurate and water up to a viscosity of 20-30 mPas at 25 ° C. become a coating material processed. This is applied to tin-coated steel plates by means of spin-coating in such a way that a 5 / im thick layer is created. The plates are heated ^{to 180 ° C. for 30 minutes.} In the MEK rub test described above, the coating shows no change.

Example 17: Hardening of a salt according to the invention by simple heating, ie without the addition of an aminoplast, phenoplast or blocked isocyanate. The product according to Example 11 is diluted with water to a viscosity of 20-30 mPa s at 25 ^° C. and applied to steel plates coated with tin by means of spin coating so that a 4 μm thick layer is formed.

The coating is heated at 215 ° C. for 10 minutes and cured in this way. In the MEK rub test described above and in the pasteurization in water, the coating shows no change.

Claims (11)

Claims R is an aliphatic, aromatic or araliphatic bi- or trivalent hydrocarbon radical with up to 10 carbon atoms, the one may contain another group -Y (M), 2 3 3 R is a hydrogen atom or C, -alkyl, one of R and R is Hydroxyl group and the other is a hydrogen or halogen atom, C, -alkyl or C_, -alkenyl and the R independently of one another a hydrogen or halogen atom, C, - Alkyl or C, -alkenyl, 5
R to a ring carbon atom ortho or para to the hydroxyl 3 3 Representing group R or R is bonded and a hydrogen or Halogen atom, C ₄ ~ alkyl, C, -alkenyl, -CH (R) 0H, -CH (R) 0R or a group of the formula II -CH-NR - (Y ") (M) I ₂ I s st R R (II) represents R is the remainder of a polyepoxide after removal of (m + p) 1,2-epoxide groups means, -ζί- the R independently of one another a hydrogen atom or a covalent one Represent a bond to the group R, where a cycloaliphatic ring is formed which can be substituted by one or more aliphatic, cycloaliphatic and / or heterocyclic groups, R C, .- alkyl or alkoxyalkyl with 1-6 carbon atoms each in the alkoxy and alkyl, R is the residue of a monohydric phenol, a secondary monoamine or a monocarboxylic acid after the hydrogen atom has been removed phenolic hydroxyl group, the secondary amino group or the carboxylic acid group, m 1, 2, 3 or 4, η zero or 1 and ρ means zero or 1, so that (m + p) at least 2 and at most t is 1 or 2, XC _{1 is} o-alkylene, C, - alkylidene, a carbonyl or sulfonyl group, an oxygen or sulfur atom or the direct bond, M is a hydrogen ion, a cation derived from an alkali metal, ammonia or an amine, including quaternary ammonium cations, or represents a valence of a multivalent cation, with the proviso that at least 25% of the M ions cations of the type mentioned s is 1 or 2 and Y is an anion of the formulas III, IV or V -0-s ((III), -Y (IV) or -Y (V) · N) OH 0 ~ represents. 2. Salts according to claim 1, wherein R is a radical with an average Represents molecular weight from 1000 to 500G. -yS- 3 3. Salts according to claim 1, wherein R is a hydrogen atom and R C 1, -alkylene, C, -alkylidene or arylene, aralkylidene or aralkylene represent with up to 10 carbon atoms. 4. Salts according to claim 1 of the formulas VI or VII R ⁵ 3 4 «; · -. Oh oh _R ³ _ / \ S VoCH ₀ CHCH ₀ -R -CH-CHCH 9 β + · · L RR ² _R 3_ /%. J V / T, T, (M ⁺ ) (Υ ^ϋ "> —R ^1- -N-CHT R (R ) ^{St S} II _{2 2} RR 3 / K S ~ \ T 10 Τ 9 R - · (Jl_ _Y _X; -OCH CHCH -R -CH CHCH R \ τ -— X- ^ / 2 2 / Z -ljI-Ck R ⁴ (R ⁴ ) 1233459 + wherein R, R, R, R, R, R, R, R, X, Y, M, s and t die in Claim 1 have the meaning given and R is the radical of an aliphatic, cycloaliphatic or aromatic diglycidyl ether or diglycidyl ester after removal of both glycidyl groups. 2 4 5. Salts according to claim 1, worm R and R each a hydrogen atom represent. 6. Process for the preparation of water-soluble or water-dispersible salts, characterized in that a resin is used with terminal phenol groups of the formula IX -CH-CII- -R Jp H- HO < -OH (IX), worm
4th
the R independently of one another a hydrogen or halogen atom, C, _ / - alkyl or C __, - alkenyl and R the remainder of a polyepoxide after removing (m + p) 1,2-epoxy groups mean the R independently of one another a hydrogen atom or a covalent one Represent a bond to the group R, forming a cycloaliphatic ring which is formed by one or more aliphatic, substituted cycloaliphatic and / or heterocyclic groups can be, 9
R is the residue of a monohydric phenol, a secondary monoamine or a monocarboxylic acid after removal of the hydrogen atom of the phenolic hydroxyl group, the secondary amino group or the carboxylic acid group,
m 1, 2, 3 or 4,
η zero or 1 and ρ represent zero or 1 such that (m + p) at least 2 and at most 4 is X C - ^ - alkylene, C-jo-alkylidene, a carbonyl or sulfonyl group, means an oxygen or sulfur atom or the direct bond, with the proviso that at least one of the two carbon atoms in the ortho position or the carbon atom in the para position to the carbon atom bearing the specified phenolic hydroxyl group is unsubstituted,
in CiGjVMiwnrt of an M -Clone-releasing agent with an aldehyde of Fo L-iiiul X - R CHO (X) and an aminosulfonic acid or an aminophosphonic acid of Formula XI HN-R. -YII (XI) implements, whereby R is a hydrogen atom or C, -alkyl, 2
R represents a hydrogen atom or C, alkyl and M represents a hydrogen ion, a cation derived from an alkali metal, ammonia or an amine, including quaternary ammonium cations, or a valence of a polyvalent cation, with the proviso that at least 25% of the M ions cations of said Kind are R _{1 represents} an aliphatic, aromatic or araliphatic divalent or trivalent hydrocarbon radical with up to 10 carbon atoms, which can contain a free phosphonic acid or sulfonic acid group of the formula -S (: OlOH or -P (: 0) (0H) _{2 and Y denotes} Means residue of a sulfonic acid or phosphonic acid after removal of a hydrogen atom. 7. The method of claim 6, wherein R is a radical having an average Represents molecular weight from 1000 to 5000. 8. The method according to claim 6, characterized in that 0.3 to 2.0 moles of the amino acid of the formula XI are used per mole of phenolic hydroxyl groups in the resin of the formula IX. 33102G7 -Iß- ^fc 9. The method according to claim 6, characterized in that 1.1 to 4.0 moles of the aldehyde of the formula X per mole of acid of the formula XI is used. 10. Heat-curable compositions of matter containing 100 parts by weight of a salt of the formula I according to claim 1 or of a salt prepared according to claim 6 and 2 to 200 parts by weight of an aminoplast, a phenol-formaldehyde resin or a blocked polyisocyanate, the parts by weight mentioned being based on the solids content of the Relate composition of matter and the aminoplast or the phenol-formaldehyde resin at least two groups of the formula (XVI) have which are attached directly to amide nitrogen atoms or to carbon atoms 14th of a phenolic ring are bonded, and where R is a hydrogen atom or C ₁ , -alkyl.
1 — ö 11. A method for coating surfaces, characterized in that that a composition of matter according to claim 10 or, in the absence of an aminoplast, a phenol-formaldehyde resin, is applied to the surface or of a blocked polyisocyanate, a salt of the formula I 5 2 applied according to claim 1, wherein R is -CH (R) 0H, and the coated surface heated to 100 to 275 ° C to harden the composition of matter or the salt.